U.S. patent application number 14/088499 was filed with the patent office on 2015-05-28 for halogen-free high-frequency resin composition.
The applicant listed for this patent is ITEQ CORPORATION, ITEQ (DONGGUAN) CORPORATION. Invention is credited to Yongxin Jiang, Hailin Li, Feng Tang, Faquan Tu, Tsung-Lieh Weng, Quansheng Zhu.
Application Number | 20150147799 14/088499 |
Document ID | / |
Family ID | 53182992 |
Filed Date | 2015-05-28 |
United States Patent
Application |
20150147799 |
Kind Code |
A1 |
Li; Hailin ; et al. |
May 28, 2015 |
HALOGEN-FREE HIGH-FREQUENCY RESIN COMPOSITION
Abstract
Disclosed is a halogen-free high-frequency resin composition
calculated according to parts by weight, and including 20-50 parts
by weight of dicyclopentadiene epoxy resin, 10-40 parts by weight
of styrene-maleic anhydride copolymer, 10-30 parts by weight of
benzoxazine resin, 5-20 parts by weight of polyfunctional epoxy
resin and 20-40 parts by weight of at least one
phosphorus-containing flame retardant. A copper clad laminate made
of the halogen-free high-frequency resin composition has excellent
properties including a low dielectric constant, a low dielectric
loss, a high heat resistance, a low water absorption, a low
coefficient of expansion and a high PCB manufacturability.
Inventors: |
Li; Hailin; (Dongguan City,
CN) ; Tu; Faquan; (Dongguan City, CN) ; Weng;
Tsung-Lieh; (Dongguan City, CN) ; Jiang; Yongxin;
(Dongguan City, CN) ; Tang; Feng; (Dongguan City,
CN) ; Zhu; Quansheng; (Dongguan City, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ITEQ CORPORATION
ITEQ (DONGGUAN) CORPORATION |
Ping Chen
Dongguan City |
|
TW
CN |
|
|
Family ID: |
53182992 |
Appl. No.: |
14/088499 |
Filed: |
November 25, 2013 |
Current U.S.
Class: |
435/196 ;
524/508; 525/117 |
Current CPC
Class: |
C08L 63/00 20130101;
H05K 1/0326 20130101; C08L 61/06 20130101; C08L 79/04 20130101;
H05K 1/0373 20130101; C08L 25/08 20130101; H05K 2201/0209 20130101;
C08L 25/08 20130101; C08L 61/06 20130101; C08L 63/00 20130101; C08K
3/36 20130101; C08L 79/04 20130101; H05K 2201/012 20130101; C08G
59/3218 20130101; C08K 3/36 20130101; C08L 63/00 20130101 |
Class at
Publication: |
435/196 ;
525/117; 524/508 |
International
Class: |
C08L 63/00 20060101
C08L063/00; C12N 9/16 20060101 C12N009/16; H05K 1/03 20060101
H05K001/03; C08L 25/08 20060101 C08L025/08; C08L 71/00 20060101
C08L071/00 |
Claims
1. A halogen-free high-frequency resin composition, comprising:
20-50 parts by weight of a dicyclopentadiene epoxy resin; 10-40
parts by weight of a styrene-maleic anhydride copolymer; 10-30
parts by weight of a benzoxazine resin; 20-40 parts by weight of at
least one phosphorus-containing flame retardant; and 5-20 parts by
weight of a polyfunctional epoxy resin; wherein, the molecular
structural formula of the dicyclopentadiene epoxy resin is:
##STR00004## and the molecular structural formula of the
styrene-maleic anhydride copolymer is: ##STR00005## and
m:n=3:1.
2. The halogen-free high-frequency resin composition of claim 1,
wherein the benzoxazine resin includes one or more resins selected
from the group consisting of a bisphenol-A benzoxazine resin, a
bisphenol-F benzoxazine resin, and a phenolphthalein benzoxazine
resin.
3. The halogen-free high-frequency resin composition of claim 1,
wherein the phosphorus-containing flame retardant includes one or
more compounds selected from the group consisting of a phosphatase,
a phosphazene compound, a phosphaphenanthrene and a derivative
thereof.
4. The halogen-free high-frequency resin composition of claim 1,
wherein the polyfunctional epoxy resin includes one or more epoxy
resins selected from the group consisting of a trifunctional epoxy
resin, a biphenyl epoxy resin, and a naphthalene ring epoxy
resin.
5. The halogen-free high-frequency resin composition of claim 1,
further comprising one or more organic fillers selected from the
group consisting of crystalline silica, melted silica, spherical
silica, kaolin and talcum powder.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a halogen-free
high-frequency resin composition.
BACKGROUND OF THE INVENTION
[0002] The RoHs and WEE directives on the restriction and
prohibition of the use of certain hazardous substances in
electrical and electronic equipment were adopted by the European
Union in February 2003, and the former relates to the directive of
restricting and prohibiting the use of certain toxic, hazardous
substances and elements of electrical and electronic equipments and
the later relates to the directive of recycling waste electrical
and electronic equipments. The WEEE directive took effect on August
2005 and the RoHs directive took effect on July 2006. To pass new
standards of this sort, the use of traditional halogen-containing
flame retardant materials should be reduced slowly until they are
eliminated. In addition, the combustion of halogen-containing flame
retardants or resins produces a large quantity of smoke and toxic
and corrosive gases, which jeopardize human body and environment
substantially. In particular, the European Union restricts the
application of halogen flame retardants in electronic and circuit
industries by laws, so that it is imperative to develop
halogen-free green clad copper laminates.
[0003] After the aforementioned two European Union's directives
were promulgated, printed circuit board manufacturers also request
clad copper laminate manufacturers to develop halogen-free green
clad copper laminate substrates. At present, the electronic
industry blooms, and the performance requirements of clad copper
laminates becomes increasingly higher, particularly for three major
portable electronic products, satellite transmission and
communication electronic products. The factors affecting the
performance of the aforementioned products basically include the
dielectric coefficient (Dk) and the dielectric loss tangent (Df) of
the substrate. The smaller the dielectric coefficient of the
substrate, the faster the signal transmission rate, the smaller the
dielectric loss tangent value, the more complete the signal
transmission, and the higher the signal authenticity. Particularly,
present electronic products are developed with a light, thin and
compact design and an increasingly higher transmission rate (over 1
GHz), and it is a main subject for related manufacturers to develop
high-performance halogen-free high-frequency printed circuit
board.
[0004] On the other hand, the conventional lead-free high-frequency
printed circuit board generally uses bromine for flame retardation,
but carbon-bromide (C--Br) bonds with low bond energy may be broken
easily at high temperature, and thus causing the delamination of
the substrate. Therefore, insufficient heat resistance becomes a
major issue in the manufacture of circuit boards. Particularly, the
present high-density interconnects (HDI) technology has
increasingly higher requirements, and the issue of insufficient
heat resistance limits the development of the HDI technology,
particularly the high-frequency HDI technology. In addition, the
present electronic products require the properties of high density
and high reliability, and thus the substrate must have excellent
hear resistance, low coefficient of expansion, chemical resistance,
and dimension stability, so that the development of high-frequency
printed circuit boards with high heat resistance and low
coefficient of expansion becomes a trend of developing
high-frequency substrates.
SUMMARY OF THE INVENTION
[0005] In view of the aforementioned shortcomings of the prior art,
it is a primary objective of the present invention to overcome the
shortcomings by providing a halogen-free high-frequency resin
composition, so that the manufactured clad copper laminate features
the advantages of lower dielectric constant and dielectric loss,
excellent heat resistance, good manufacturability and low
coefficient of expansion and meets the halogen-free environmental
protection requirements.
[0006] To achieve the aforementioned objective, the present
invention provides a halogen-free high-frequency resin composition,
comprising: 20-50 parts by weight of a dicyclopentadiene epoxy
resin; 10-40 parts by weight of a styrene-maleic anhydride
copolymer; 10-30 parts by weight of a benzoxazine resin; 20-40
parts by weight of at least one phosphorus-containing flame
retardant; and 5-20 parts by weight of a polyfunctional epoxy
resin; and the molecular structural formula of the
dicyclopentadiene epoxy resin is shown below:
##STR00001##
[0007] The molecular structural formula of the styrene-maleic
anhydride copolymer is shown below:
##STR00002##
[0008] Where, m:n=3:1.
[0009] The benzoxazine resin is one or more resin selected from the
group consisting of a bisphenol-A benzoxazine resin, a bisphenol-F
benzoxazine resin, and a phenolphthalein benzoxazine resin.
[0010] The phosphorus-containing flame retardant includes one or
more compounds selected from the group consisting of a phosphatase,
a phosphazene compound, a phosphaphenanthrene and a derivative
thereof.
[0011] The polyfunctional epoxy resin includes one or more epoxy
resins selected from the group consisting of a trifunctional epoxy
resin, a biphenyl epoxy resin, and a naphthalene ring epoxy
resin.
[0012] Compared with the prior art, the present invention has the
following advantages and effects:
[0013] 1. The use of the dicyclopentadiene epoxy resin is capable
of providing a lower dielectric constant, and the existence of
dicyclopentadiene can provide excellent heat resistance and
manufacturability for circuit boards.
[0014] 2. The styrene-maleic anhydride copolymer having the
anhydride structure can react with epoxy resin and also has the
benzene ring structure capable of providing the properties of high
heat resistance and low water absorption rate. Particularly a
three-dimensional interpenetrating network is formed after the
reaction to provide a lower dielectric loss value of the
material.
[0015] 3. The use of the benzoxazine resin with a specific flame
retardation effect can assist the phosphorus-containing flame
retardant for the flame retardation and reduce the consumption of
the phosphorus-containing flame retardant (since the
phosphorus-containing flame retardant absorbs moisture easily, so
that the substrate may be delaminated easily), so as to reduce the
water absorption rate and the risk of delamination. In addition,
the resin of this type further has a good dielectric performance
and its cured product has a good PCB manufacturability.
[0016] 4. The composition of the present invention has a
polyfunctional epoxy resin capable of reducing the coefficient of
expansion of the substrate significantly and improving the
manufacturability and reliability of the substrate.
[0017] 5. The laminates made of this resin composition has the
properties of low dielectric constant, low dielectric loss value,
high heat resistance, and low water absorption to overcome the
shortcomings including the poor heat resistance, high water
absorption rate, and poor PCB manufacturability of the conventional
high-frequency clad copper laminate, so that the laminates can have
good applications in multi-layer boards.
[0018] 6. Inorganic materials are added to lower the cost, and the
inorganic filler such as silicon dioxide can reduce the coefficient
of expansion and improve the heat resistance and flame retardation
effects.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] None
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] The aforementioned and other objectives and advantages of
the present invention will become clearer in light of the following
detailed description of an illustrative embodiment of this
invention described in connection with the drawings. It is intended
that the embodiments and drawings disclosed herein are to be
considered illustrative rather than restrictive.
[0021] The aforementioned properties are described by the following
embodiments and examples of a control group, and Embodiments 1-7
and Examples of a control group 1-3 are described below.
[0022] The proportion of related substances divided into organic
matters, respectively A1, A2, A3, B1, B2, C1 and C2, D calculated
according to 100 parts by weight, and the percentage occupied by
other compositions is the total weight percentage of the organic
matters.
[0023] (A1) Styrene-maleic anhydride copolymer, SMA-EF30
(m:n=3:1)
[0024] (A2) Phenolphthalein benzoxazine
[0025] (A3) Bisphenol A benzoxazine
[0026] (B1) Dicyclopentadiene (modified DCPD) epoxy resin
[0027] (B2) Trifunctional epoxy resin
[0028] (C1) Phosphorus-containing phenolic resin
[0029] (C2) Phosphatase
[0030] (D) Melted silica power
[0031] The molecular structural formula of the trifunctional epoxy
resin is shown below:
##STR00003##
[0032] The laminate substrate of the present invention is produced
by the aforementioned halogen-free high-frequency resin composition
which is melted, dipped, glued, heated, and laminated. In the
gluing process, a fiberglass cloth with the 2116 specification, a
lamination specification of 2116*6 ply, and a thickness
approximately equal to 0.8 mm. In addition, a copper foil with a
thickness of 35 um (or a weight of 1 oz) is used for the
lamination, and the copper foil is produced and pressed by a hot
press machine, and the temperature of the material is controlled
above and maintained for 100 min.
TABLE-US-00001 Recipe of Composition (1) calculated according to
parts by weight Embodi- Embodi- Embodi- Embodi- Embodi- ment 1 ment
2 ment 3 ment 4 ment 5 A1 20 20 15 20 10 A2 18 18 18 28 A3 18 B1 30
30 40 25 30 B2 10 10 5 15 10 C1 22 22 22 22 C2 22 D 25 25 25 25
25
TABLE-US-00002 Recipes of the Composition calculated according to
parts by weight Table (2) Embodi- Embodi- Embodi- Example 1 Example
2 ment 6 ment 7 ment 8 of Control of Control A1 36 14 15 35 A2 11
12 18 30 30 A3 5 B1 26 26 30 35 B2 6 10 10 10 10 C1 21 28 22 25 25
C2 10 D 25 25 25 25 25
TABLE-US-00003 Recipe Performance Evaluation Table (1) Condition
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Glass transition .degree. C. 194 170 175 155 186 temperature (Tg,
.degree. C., DSC) Thermal min >60 >60 >60 >60 >60
stratification time T-288.degree. CTMA (containing cupper) Peeling
Strength N/mm 1.2 1.2 1.2 1.1 1.2 (1 oz) Water absorption % 0.37
0.41 0.37 0.35 0.38 (PCT1h) PCT 1h + dip (Dip) min >10 >10
>10 >10 >10 Coppery clad min >30 >30 >30 >30
>30 floating solder coefficient of % 2.5 2.8 2.8 2.6 2.5 thermal
expansion Z-axis CTE (%) Flame retardation UL94 V-0 V-0 V-0 V-0 V-0
dielectric constant 1 GHz 3.85 3.78 3.71 3.83 3.86 Dielectric loss
1 GHz 0.0055 0.0054 0.0059 0.0048 0.0062 value Halogen content %
0.03 0.03 0.03 0.03 0.03
TABLE-US-00004 Recipe Performance Evaluation Table (2) Embodiment
Embodiment Embodiment Example 1 Example 2 Condition 6 7 8 of
Control of Control Glass transition .degree. C. 179 180 180 191 201
temperature (Tg, .degree. C.) Thermal layer min >60 >60
>60 45 40 division time T-288.degree. CTMA (containing copper)
Peeling N/mm 1.2 1.2 1.2 1.4 1.4 strength(1 oz) Water absorption %
0.38 0.42 0.42 0.48 0.52 PCT 1h + Dip min >10 >10 >10
>10 >10 Copper clad min >30 >30 >30 18 15 floating
solder Coefficient of % 2.4 2.7 2.7 3.1 3.3 thermal expansion
Z-axis CTE(%) Flame retardation UL94 V-0 V-0 V-0 V-1 V-1 Dielectric
constant 1 GHz 3.89 3.83 3.82 4.15 4.30 Dielectric loss 1 GHz
0.0045 0.0063 0.0060 0.0092 0.0095 constant Halogen content % 0.03
0.03 0.03 0.03 0.03
[0033] The testing methods of the aforementioned properties are
described below:
[0034] (1) Water absorption percentage: It is a percentage of the
weight difference before and after the PCT steaming process with
respect to the sample weight before the PCT takes place.
[0035] (2) Thermal layer division time: The delamination layer
division time is recorded, after the PCT is steamed for an hour at
121.degree. C. in 105 KPa pressure cooker, and dipped in the solder
pot at 288.degree. C.
[0036] (3) Copper clad floating solder: The delamination time is
measured when the solder (at 288.degree. C.) of a copper clad
laminate floats on a solder pot.
[0037] (4) Thermal layer division time T-288: It is measured
according to the IPC-TM-650 2.4.24.1 method.
[0038] (5) Coefficient of thermal expansion Z-axis CTE (TMA): It is
measure according to the IPC-TM-650 2.4.24 method.
[0039] (6) Glass transition temperature (Tg): It is measured
according to the differential scanning calorimetry (DSC) and the
DSC method as set forth by the IPC-TM-6502.4.25 regulation.
[0040] (7) Dielectric constant and dielectric loss value: Both
dielectric constant and dielectric loss value are measured below
GHz by a parallel board method according to the IPC-TM-6502.5.5.9
regulation.
[0041] (8) Peeling strength: It is measured according to the
IPC-TM-650 2.4.9 regulation.
[0042] (9) Combustibility: It is measured by a vertical combustion
method according to the UL 94 regulation.
[0043] According to the aforementioned results, the laminates
produced by the composition of the present invention feature low
dielectric constant, low dielectric loss, low coefficient of
expansion, high heat resistance, low water absorption, and
refractory function, while providing excellent manufacturability.
Further, the halogen content is less than 0.09%, thus achieving
halogen-free flame retardations and meeting environmental
protection requirements. In addition, the printed circuit boards
produced by the composition of the present invention feature high
heat resistance, excellent high-frequency dielectric property, and
capability of meeting the increasingly higher requirement of the
printed circuit boards for high-frequency transmission systems.
[0044] While the invention has been described by means of specific
embodiments, numerous modifications and variations could be made
thereto by those skilled in the art without departing from the
scope and spirit of the invention set forth in the claims.
* * * * *